α-丙氨酸Co^(3+)配合物旋光异构及水溶剂效应的理论研究  

Theoretical Study on the Optical Isomerism and Aqueous Solvent Effect ofα-Ala·Co^(3+)Complexes

作　　者：彭国强[1] 刘军[2] 徐锐英[2] 雷泽平 杨清荟 崔金玉 赵丽红[1] 郝成欣[1] 王佐成[2] 佟华[2] PENG Guoqiang;LIU Jun;XU Ruiying;LEI Zeping;YANG Qinghui;CUI Jinyu;ZHAO Lihong;HAO Chengxin;WANG Zuocheng;TONG Hua(Department of Basic Medicine,Baicheng Medical College,Baicheng Jilin 137000,China;College of Physics,Baicheng Normal University,Baicheng Jilin 137000,China;Basic Courses Teaching and Research Department,Yingkou Institute of Technology,Yingkou Liaoning 115000,China)

机构地区：[1]白城医学高等专科学校基础医学部,吉林白城137000 [2]白城师范学院物理学院,吉林白城137000 [3]营口理工学院基础教研部,辽宁营口115000

出　　处：《复旦学报（自然科学版）》2021年第5期607-617,共11页Journal of Fudan University：Natural Science

基　　金：吉林省教育厅科学研究项目(JJKH20210010KJ);吉林省大学生创新项目(202110206019);吉林省自然科学基金项目(20130101308JC)。

摘　　要：采用密度泛函理论的M06和MN15方法,研究了α-丙氨酸(α-Ala)与Co^(3+)配合物的旋光异构及水溶剂效应.反应通道的研究结果显示:气相α-Ala·Co^(3+)可在2个通道a和b实现旋光异构,a是羰基氧作质子迁移媒介;b是羰基氧和甲基碳联合作质子迁移媒介.水液相下α-Ala·Co^(3+)可在3个通道a、b和c实现旋光异构,a和b通道与气相的相同;c是羰基氧和氨基氮联合作质子迁移媒介.势能面计算结果表明:气相α-Ala·Co^(3+)在a和b通道旋光异构的活化能都是113.2 kJ·mol^(-1);隐性水溶剂效应下α-Ala·Co^(3+)在a、b和c通道旋光异构的活化能都是235.6 kJ·mol^(-1),显性水溶剂效应下该能垒降到143.5 kJ·mol^(-1).结果表明:气相α-Ala·Co^(3+)可以缓慢地消旋,水液相下的α-Ala·Co^(3+)很难消旋.The optical isomerism and aqueous solvent effect ofα-alanine(α-Ala)complexes with Co^(3+)have been studied by using the M06 and MN15 methods based on density functional theory.The study results of reaction channels shows thatα-Ala·Co^(3+)in gas phase can achieve optical isomerization in two channels a and b,the carbonyl O atom as the protolysis medium in channel a;the combination of carbonyl O atom and methyl C atom as the protolysis medium in channel b.Theα-Ala·Co^(3+)can achieve optical isomerization in three channels a、b and c in aqueous phase,and the channels a and b are the same as those in gas phase;the combination of carbonyl O atom and amino N atom as the protolysis medium in channel c.The calculation of potential energy surface shows that the optical isomerism ofα-Ala·Co^(3+)in channels a and b in gas phase have the same activation energy(113.2 kJ·mol^(-1));under the effect of recessive solvent,the channels a、b and c of theα-Ala·Co^(3+)optical isomerization have the same activation energy(235.6 kJ·mol^(-1)),the effect of explicit slovent reduces the energy barrier to 143.5 kJ·mol^(-1).The results show thatα-Ala·Co^(3+)can racemize slowly in gas phase,but it is difficult to racemize in the water-liquid phase.

关 键 词：Α-丙氨酸 三价钴离子 密度泛函理论 旋光异构 溶剂效应 能垒 

分 类 号：O641.12[理学—物理化学]